2 Introduction Source receptor modeling using the Chemical Mass Balance (CMB) model requires source fingerprints. To better understand the sources of fine particulate matter in Pittsburgh region, PM 2.5 fingerprints were developed for urban and rural road dust. Samples were analyzed for OC/EC, elemental composition, and organic species. An important contribution of this work is the development of the first road dust finger print with speciated organics information outside of the Los Angeles basin.

3 Road Dust Collection Sampling Locations Sampling Locations Road dust samples were collected from 5 rural and 6 urban/suburban sites using a vacuum sampler constructed out of Teflon and stainless steel. Samples were dried in an oven at 100 C and then passed through a 37 µm sieve to remove large particles. The samples were combined to create a composite urban and rural dust sample. Samples were collected in the summer of Road dust collection at a rural site.

6 Speciated Organic Composition n-alkanoic Acids n-alkanes PAH Hopanes Streanes n-alkenoic Acids Steroids Thiazoles Alkylcyclohexanes Resin Acids P. Triterpenoids (a) Major Classes (b) Minor Classes GC-MS analysis was performed on solvent extracted samples to quantitatively determine contribution of more than 100 individual organic species to the road dust. Figure 3 shows the contribution of different compound classes to the road dust OC. In total, the identified compounds contribute 0.35% and 0.94% of the OC mass in the rural and urban road dust samples, respectively. For most of the compound classes, the urban road dust is significantly enriched compared to the rural sample. For example, the contribution of n-alkanes to the urban sample is almost a factor of 4 greater than in the rural sample. The notable exception to this is the enrichment of steroids (cholesterol and beta-sitosterol) in the rural sample Figure 3. Contribution of major compound classes to OC.

11 Steroids Dehydroabietic Acid b-sitosterol Cholesterol Figure 8 compares urban and rural road dust steroid and dehydroabietic acid levels. Dehydroabietic acid is a tracer of soft wood combustion and cholesterol is a marker for meat cooking emissions. Beta-sitosterol is a plant derived sterol, also known as a phytostero. Beta-sitosterol is measured in soft-wood smoke and is also found in plant abrasion products Figure 8. Road dust steroids and resin acids. The two steroids are the only quantified compounds that were enriched in the rural road dust relative to the urban wood dust. We interpret this as the rural road dust being enriched in material of biological origin.

12 Comparison with Los Angeles Road Dust (a) Major Classes n-alkanoic Acids n-alkanes (b) Minor Classes PAH Hopanes Steranes n-alkenoic Acids Thiazoles Resin Acids LA Oxy-PAH Pittsburgh Figure 9. Pittsburgh and LA road dust. Rogge et al. (1993) measured the organic molecular composition of a road dust sample collected in Los Angeles. OC contributes approximately 13% of the PM 2.5 mass in both the Pittsburgh and LA road dust samples. EC levels in the two samples are also comparable (~ 1% of PM 2.5 mass). Figure 9 compares the contribution of major organic classes to the OC in the of the Pittsburgh urban sample and the Los Angeles sample. The distribution of compounds within these classes is generally similar between the two samples. Los Angeles road dust is enriched in most of the compound classes compared to Pittsburgh. For example, alkanoic acids and n-alkanes are more than a factor of 5 higher in the LA samples. Hopanes and steranes are enriched by a factor of ~ 1.5 in the LA samples suggesting a large contribution of vehicular emissions to road dust in LA. PAH and thiazoles are the only two compounds classes that are elevated in Pittsburgh road dust compared to LA. The enrichment of PAH is likely due to differences in the industrial sources between Pittsburgh and LA. A much larger fraction of the OC in LA road dust was identified on a compound by compounds basis compared to Pittsburgh (5% in LA versus 0.9% in Pittsburgh).

13 Conclusions Significant differences were observed in the composition of urban and rural road dust elevated in vehicular markers and metals associated with anthropogenic sources elevated in markers for biological material In sum, the identified organic species contributed less than 1% of the OC mass Acknowledgments: This research was conducted as part of the Pittsburgh Air Quality Study, which was supported by US Environmental Protection Agency under contract R and the US Department of Energy National Energy Technology Laboratory under contract DE-FC26-01NT This poster has not been subject to EPA's peer and policy review, and therefore does not necessarily reflect the views of the Agency. No official endorsement should be inferred.

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